CN108585794A - A kind of chromium manganese is total to occupy-place Ca-Ti ore type negative temperature coefficient thermal-sensitive ceramic material - Google Patents
A kind of chromium manganese is total to occupy-place Ca-Ti ore type negative temperature coefficient thermal-sensitive ceramic material Download PDFInfo
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Abstract
The present invention provides a kind of preparation methods of Fe2O3 doping Ca-Ti ore type negative temperature coefficient thermal-sensitive ceramic material：By La:Cr:Mn atomic percents are 20 55:5‑75:5 40, which weigh raw material, carries out wet-milling, obtains slurry；Powder is obtained after slurry drying and grinding；It calcines again, obtains La (CrMn) O of Perovskite Phase3Powder；Powder is prepared into after block materials and uses two-step sintering method, furnace cooling obtains Fe2O3 doping Ca-Ti ore type negative temperature coefficient thermal-sensitive ceramic material.The chromium manganese obtained by this method is total to the electrical parameter of occupy-place Ca-Ti ore type negative temperature coefficient thermal-sensitive ceramic material：ρ 25°C=15.2 Ω cm 13823.2K Ω cm ± 2%, B25/50=2688 3942K ± 1.5%, the material have the characteristics that high resistant, low B and low-resistance, the parameter combination of high B, consistency is good, stability is high, repeatable, are respectively suitable for the measurement, control of temperature in wide warm area, line build-out and inhibit surge current.
Description
Technical field
The invention belongs to novel thermosensitive ceramic material fields, and in particular to a kind of using oxide solid phase method to prepare chromium manganese total
The method of occupy-place Ca-Ti ore type negative temperature coefficient thermal-sensitive ceramic material.
Background technology
Negative temperature coefficient（NTC）Thermistor, because it is high with temperature measurement accuracy, interchangeability is good, reliability is high, of low cost
The advantages that, it is widely used, is recognized in various aspects such as the remote controls of temperature measurement, control, compensation and communication apparatus
To be the electronic component with tremendous expansion potentiality, there is good application prospect.Usual AB2O4Type spinel structure is NTC
The principal crystalline phase of thermal sensitive ceramic material, with the development of science and technology and demand, the limitation of this kind of material becomes increasingly conspicuous.When the electricity of material
Its B value is also high when resistance rate is higher, and vice versa, while the stability of the polynary series ceramic material of spinel structure composition is poor,
Sintered ceramics are in nonequilibrium condition, cause material electric property to change, constrain spinelle NTC temperature-sensitive elements at this 2 points
Application, the key for solving the problems, such as this is to explore new NTC thermal sensitive ceramic materials.
Perovskite structure（ABO3）Ceramic Lanthanum Chromite（LaCrO3）With lanthanum manganate（LaMnO3）Because having giant magnetoresistance（GMR）Effect
It answers, sense and catalytic performance, and in solid oxide fuel cell connecting material, high temperature exothermic material, catalyst etc.
It is up-and-coming ceramic material to being widely applied.But the research in terms of as NTC thermistor material and application
Seldom, Lanthanum Chromite has good high-temperature stability with lanthanum manganate, and has NTC characteristics in certain temperature range, passes through skill
Art processing is expected to replace traditional Spinel, solves above-mentioned NTC thermal sensitive ceramic materials problems faced.LaCrO3With high
Resistivity, and its electric conductivity is by the Modulatory character of Doped ions and environment height；LaMnO3With good electric conductivity, room temperature electricity
Resistance rate is less than 1 Ω cm.Perovskite ABO is accounted for altogether by compound realization chromium manganese3The positions B, and then regulate and control its unit for electrical property parameters, obtain
It is high resistant, low B and low-resistance, high B, the NTC thermistor material that stability is good, consistency is good to obtain parameter against gesture to change.
Invention content
For the problem that lacking high-precision, high resistant, low B and low-resistance, high B components at present, the present invention provides a kind of chromium manganese
Occupy-place Ca-Ti ore type negative temperature coefficient thermal-sensitive ceramic material altogether, unit for electrical property parameters is adjustable, and stability is good, consistency is good.
It is a further object of the present invention to provide a kind of preparation methods of above-mentioned thermal sensitive ceramic material.
To achieve the above object, the present invention adopts the following technical scheme that.
A kind of chromium manganese is total to the preparation method of occupy-place Ca-Ti ore type negative temperature coefficient thermal-sensitive ceramic material, includes the following steps：
（1）By La:Cr:Mn atomic percents are 20-55:5-75:5-40 weighs La2O3、Cr2O3、MnO2Wet-milling is carried out, must be starched
Material；
（2）By step（1）In slurry drying, then grind to obtain powder；
（3）By step（2）In powder calcination, obtain La (CrMn) O of Perovskite Phase3Powder；
（4）By step（3）In pressed by powder at Perovskite Phase La (CrMn) O3Block materials；
（5）By step（4）In block materials be first warming up to 1350-1450 DEG C, be then cooled to 1200-1300 DEG C of heat preservation again,
I.e. obtaining chromium manganese is total to occupy-place Ca-Ti ore type negative temperature coefficient thermal-sensitive ceramic material for furnace cooling.
Step（1）In, the wet-milling is using agate ball as ball-milling medium, using absolute ethyl alcohol as decentralized medium；Agate ball:It is former
Material:Absolute ethyl alcohol mass ratio is 2.5:1:1；Preferably, wet-milling is along counterclockwise alternately, along interval time counterclockwise
30min；The wet-milling time is 10-24h.
Step（2）Middle drying temperature is 80-100 DEG C；Milling time is 1h.
Step（3）Middle calcination temperature is in 950-1050 DEG C；Calcination time is 1-3h.
Step（3）In, La (CrMn) O3Powder is single perovskite structure, D50It is 0.128-1.054 μm.The D50Refer to
Cumulative particle sizes volume percentile reaches grain size corresponding when 50%.
Step（3）Further include by Perovskite Phase La (CrMn) O3Grinding, obtains the process of even-grained powder；The powder
The D of body50It is 0.101-0.974 μm.
Step（4）In, preferred preparation method is that the disk of Φ 10mm, dwell time are pressed under the pressure of 10Mpa
For 3min, then by the disk under the pressure of 350Mpa isostatic cool pressing 4min to get.
Step（5）In, the heating rate is 5-10 DEG C/min；The temperature fall time is 1-5min；Soaking time is 5-
15h。
A kind of La (CrMn) O that the above method obtains3Ceramic material；The relative density of the ceramic material is 95.0-
97.0%；The electrical parameter of the ceramic material is：ρ 25°C=15.2-13823.2 Ω cm ± 2%, B25/50=2688-3942K±
1.5%。
The present invention has the following advantages：
When prepared by powder, the mode of abrasive material has important influence to the granularity and uniformity of powder.The present invention uses wet-milling
Mode, using absolute ethyl alcohol as ball milling decentralized medium, the ball milling under the atmosphere of liquid phase is improved due to the effect of surface tension
The ball milling activity of powder；And carried out along counter clockwise direction ball milling alternating rule during ball milling, keep ball milling more abundant, this
Powder granularity that sample obtains uniformly, good dispersion, particle size is small, and the material obtained after forming and sintering is good at porcelain, temperature-sensitive
Ceramic material consistency is good, and stability is high.
Occupy-place perovskite structure ABO is total to using chromium manganese3The positions B prepare high resistant, low B and low-resistance, high B parameter changes against gesture
Negative temperature coefficient thermal-sensitive ceramic material changes its electrical property by adjusting the relative amount with the total occupy-place ion chromium manganese of change
Parameters variation direction improves the high-temperature stability of NTC thermal sensitive ceramic materials, expands it as NTC thermistor ceramics material
The application range of material.
It is brilliant in high-temperature sintering process to avoid when preparing chromium manganese and being total to occupy-place Ca-Ti ore type negative temperature coefficient thermal-sensitive ceramic material
Grain length is big, influences its electrical property, using two-step sintering method, that is, is warming up to after maximum sintering temperature fast cooling to certain temperature,
In the low temperature long-time heat preservation, by this control to temperature, while inhibiting crystal boundary migration, grain boundary decision is kept to be in
Active state realizes the purpose that sintering is completed under the premise of crystal grain is not grown up；In addition from the angle of environmental protection, the sintering schedule energy
It is effectively energy saving.By this method be finally made crystallite dimension it is small by be evenly distributed, have high resistant, low B and low-resistance, high B parameter inverse
Gesture variation, the chromium manganese that stability is high, consistency is good are total to occupy-place Ca-Ti ore type negative temperature coefficient thermal-sensitive ceramic material, are applicable to width
The measurement, control of temperature, line build-out and inhibition surge current in warm area.
Description of the drawings
Fig. 1 is the XRD spectrum for the negative temperature coefficient thermal-sensitive ceramic material that different Mn dopings obtain；
Fig. 2 is the negative temperature coefficient thermal-sensitive ceramic material SEM pictures of embodiment 1.
Specific implementation mode
With reference to embodiment and attached drawing, the present invention will be further described, but the present invention is not limited by following embodiments
System.
Embodiment 1
（1）First with La2O3、Cr2O3、MnO2For raw material, by Perovskite Phase La (CrMn) O3Atomic percentage is La:Cr:Mn=
50:45:5, which weigh each oxide, is placed in agate jar, is decentralized medium by ball-milling medium, absolute ethyl alcohol of agate ball, wet
15h is ground, controlling each material mass ratio in ball grinder is：Agate ball:Material:Absolute ethyl alcohol=2.5:1:1, ball milling is along side counterclockwise
To alternately, along interval time 30min counterclockwise；
（2）By step（1）Slurry after middle wet-milling is dry at 80 DEG C in vacuum drying chamber, then grinds 1h and obtains powder；
（3）By step（2）In obtained powder calcine 2h at 950 DEG C, obtain La (CrMn) O of the Perovskite Phase in step a3
Powder, powder granule degree are 0.746 μm；It is subsequently placed in agate mortar and grinds 4h, obtain even-grained powder body material, powder
Granularity is 0.469 μm；
（4）By step（3）In obtained powder be pressed into the disk of Φ 10mm under the pressure of 10Mpa, dwell time 3min,
Again by the disk under the pressure of 350Mpa isostatic cool pressing 4min, obtain being molded good Perovskite Phase La (CrMn) O3Block material
Material；
（5）By step（4）In obtained block materials rise to 1400 DEG C with the rate of 10 DEG C/min, then by temperature in 4min
1250 DEG C of heat preservation 10h are rapidly decreased to, furnace cooling can be obtained chromium manganese and be total to occupy-place Ca-Ti ore type negative temperature coefficient thermosensitive ceramics material
Material, relative density 96.0%；
Obtained chromium manganese is total to occupy-place Ca-Ti ore type negative temperature coefficient thermal-sensitive ceramic material and carries out electric performance test, electrical parameter
Forρ25 °C=13823 Ω cm ± 2%, B25/50=3942K ± 1.5%；The material be suitable for the measurement of temperature under wide warm area,
Control, line build-out.Its XRD spectrum is as shown in Figure 1；Its SEM photograph is as shown in Fig. 2, crystallite dimension is small and uniform, consistency
It is high.
Embodiment 2
（1）First with La2O3、Cr2O3、MnO2For raw material, by Perovskite Phase La (CrMn) O3Atomic percentage is La:Cr:Mn=
50:15:35, which weigh each oxide, is placed in agate jar, is decentralized medium by ball-milling medium, absolute ethyl alcohol of agate ball, wet
20h is ground, controlling each material mass ratio in ball grinder is：Agate ball:Material:Absolute ethyl alcohol=2.5:1:1, ball milling is along side counterclockwise
To alternately, along interval time 30min counterclockwise；
（2）By step（1）Slurry after middle wet-milling is dry at 80 DEG C in vacuum drying chamber, then grinds 1h and obtains powder；
（3）By step（2）In obtained powder calcine 2h at 1000 DEG C, obtain the La (CrMn) of the Perovskite Phase in step a
O3 powders, powder granule degree are 0.417 μm；It is subsequently placed in agate mortar and grinds 4h, obtain even-grained powder body material, powder
Body granularity is 0.306 μm；
（4）By step（3）In obtained powder be pressed into the disk of Φ 10mm under the pressure of 10Mpa, dwell time 3min,
Again by the disk under the pressure of 350Mpa isostatic cool pressing 4min, obtain being molded good Perovskite Phase La (CrMn) O3Block material
Material；
（5）By step（4）In obtained block materials rise to 1350 DEG C with the rate of 8 DEG C/min, then by temperature in 5min
1230 DEG C of heat preservation 12h are rapidly decreased to, furnace cooling can be obtained chromium manganese and be total to occupy-place Ca-Ti ore type negative temperature coefficient thermosensitive ceramics material
Material, relative density 95.8%；
Obtained chromium manganese is total to occupy-place Ca-Ti ore type negative temperature coefficient thermal-sensitive ceramic material and carries out electric performance test, electrical parameter
Forρ 25°C=15.2 Ω cm ± 2%, B25/50=2688K±1.5%；The material is suitable for inhibiting surge current.Its XRD spectrum is as schemed
Shown in 1.
Embodiment 3
（1）First with La2O3、Cr2O3、MnO2For raw material, by Perovskite Phase La (CrMn) O3Atomic percentage is La:Cr:Mn=
50:35:15, which weigh each oxide, is placed in agate jar, is decentralized medium by ball-milling medium, absolute ethyl alcohol of agate ball, wet
For 24 hours, control each material mass ratio in ball grinder is mill：Agate ball:Material:Absolute ethyl alcohol=2.5:1:1, ball milling is along side counterclockwise
To alternately, along interval time 30min counterclockwise；
（2）By step（1）Slurry after middle wet-milling is dry at 100 DEG C in vacuum drying chamber, then grinds 1h and obtains powder；
（3）By step（2）In obtained powder calcine 2h at 900 DEG C, obtain La (CrMn) O of the Perovskite Phase in step a3
Powder, powder granule degree are 0.128 μm；It is subsequently placed in agate mortar and grinds 4h, obtain even-grained powder body material, powder
Granularity is 0.101 μm；
（4）By step（3）In obtained powder be pressed into the disk of Φ 10mm under the pressure of 10Mpa, dwell time 3min,
Again by the disk under the pressure of 350Mpa isostatic cool pressing 4min, obtain being molded good Perovskite Phase La (CrMn) O3Block material
Material；
（5）By step（4）In obtained block materials rise to 1450 DEG C with the rate of 5 DEG C/min, then by temperature in 5min
1300 DEG C of heat preservation 12h are rapidly decreased to, furnace cooling can be obtained chromium manganese and be total to occupy-place Ca-Ti ore type negative temperature coefficient thermosensitive ceramics material
Material, relative density 97.0%；
Obtained chromium manganese is total to occupy-place Ca-Ti ore type negative temperature coefficient thermal-sensitive ceramic material and carries out electric performance test, electrical parameter
Forρ 25°C=4965.0 Ω cm ± 2%, B25/50=3785K±1.5%；The material is suitable for the measurement, control of temperature under wide warm area
System, line build-out.Its XRD spectrum is as shown in Figure 1.
Embodiment 4
（1）First with La2O3、Cr2O3、MnO2For raw material, by Perovskite Phase La (CrMn) O3Atomic percentage is La:Cr:Mn=
50:25:25, which weigh each oxide, is placed in agate jar, is decentralized medium by ball-milling medium, absolute ethyl alcohol of agate ball, wet
10h is ground, controlling each material mass ratio in ball grinder is：Agate ball:Material:Absolute ethyl alcohol=2.5:1:1, ball milling is along side counterclockwise
To alternately, along interval time 30min counterclockwise；
（2）By step（1）Slurry after middle wet-milling is dry at 90 DEG C in vacuum drying chamber, then grinds 1h and obtains powder；
（3）By step（2）In obtained powder calcine 2h at 900 DEG C, obtain La (CrMn) O of the Perovskite Phase in step a3
Powder, powder granule degree are 1.054 μm；It is subsequently placed in agate mortar and grinds 4h, obtain even-grained powder body material, powder
Granularity is 0.974 μm；
（4）By step（3）In obtained powder be pressed into the disk of Φ 10mm under the pressure of 10Mpa, dwell time 3min,
Again by the disk under the pressure of 350Mpa isostatic cool pressing 4min, obtain being molded good Perovskite Phase La (CrMn) O3Block material
Material；
（5）By step（4）In obtained block materials rise to 1400 DEG C with the rate of 8 DEG C/min, then by temperature in 3min
1270 DEG C of heat preservation 15h are rapidly decreased to, furnace cooling can be obtained chromium manganese and be total to occupy-place Ca-Ti ore type negative temperature coefficient thermosensitive ceramics material
Material, relative density 96.5%；
Obtained chromium manganese is total to occupy-place Ca-Ti ore type negative temperature coefficient thermal-sensitive ceramic material and carries out electric performance test, electrical parameter
Forρ 25°C=40.9 Ω cm ± 2%, B25/50=3191K±1.5%；The material is suitable for inhibiting surge current, and XRD spectrum is as schemed
Shown in 1.
Claims (10)
1. a kind of chromium manganese is total to the preparation method of occupy-place Ca-Ti ore type negative temperature coefficient thermal-sensitive ceramic material, which is characterized in that including
Following steps：
（1）By La:Cr:Mn atomic percents are 20-55:5-75:5-40 weighs La2O3、Cr2O3、MnO2Wet-milling is carried out, must be starched
Material；
（2）By step（1）In slurry drying, then grind to obtain powder；
（3）By step（2）In powder calcination, obtain La (CrMn) O of Perovskite Phase3Powder；
（4）By step（3）In pressed by powder at Perovskite Phase La (CrMn) O3Block materials；
（5）By step（4）In block materials be first warming up to 1350-1450 DEG C, be then cooled to 1200-1300 DEG C of heat preservation again,
I.e. obtaining chromium manganese is total to occupy-place Ca-Ti ore type negative temperature coefficient thermal-sensitive ceramic material for furnace cooling.
2. preparation method according to claim 1, which is characterized in that step（1）In, the wet-milling is using agate ball as ball milling
Medium, using absolute ethyl alcohol as decentralized medium；Agate ball:Raw material:Absolute ethyl alcohol mass ratio is 2.5:1:1.
3. preparation method according to claim 2, which is characterized in that wet-milling is along counterclockwise alternately, along inverse
Hour hands interval time 30min；The wet-milling time is 10-24h.
4. preparation method according to claim 1, which is characterized in that step（2）Middle drying temperature is 80-100 DEG C；Grinding
Time is 1h.
5. preparation method according to claim 1, which is characterized in that step（3）Middle calcination temperature is in 950-1050 DEG C；
Calcination time is 1-3h.
6. preparation method according to claim 1, which is characterized in that step（3）In, La (CrMn) O3Powder is single calcium
Perovskite like structure, D50It is 0.128-1.504 μm.
7. preparation method according to claim 1, which is characterized in that step（3）Further include by Perovskite Phase La (CrMn) O3
Grinding, obtains the process of even-grained powder.
8. preparation method according to claim 1, which is characterized in that step（5）In, the heating rate be 5-10 DEG C/
min；The temperature fall time is 1-5min；Soaking time is 5-15h.
9. La (CrMn) O that a kind of method as described in claim 1-8 is any obtains3Ceramic material.
10. La (CrMn) O according to claim 93Ceramic material, which is characterized in that relative density 95.0-97.0%.
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| CN112876232A (en) * | 2021-01-26 | 2021-06-01 | 南京理工大学 | High-temperature NTC thermal sensitive ceramic material and discharge plasma sintering method thereof |
| CN115925418A (en) * | 2022-12-14 | 2023-04-07 | 肇庆市金龙宝电子有限公司 | Low-temperature NTC thermistor ceramic and preparation method thereof |
| WO2023093221A1 (en) * | 2021-11-29 | 2023-06-01 | 湖南纳金新材料技术有限公司 | Preparation method for high-stability low-loss microwave dielectric ceramic material, and microwave dielectric ceramic material prepared by applying same |
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| CN115925418A (en) * | 2022-12-14 | 2023-04-07 | 肇庆市金龙宝电子有限公司 | Low-temperature NTC thermistor ceramic and preparation method thereof |
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